Polymethine dyestuffs



Patented Aug. 10, 1937 PATENT OFFICE POLYMETHINE DYESTUFFS Paul Wolif and Gustav Schafer, Frankfort-onthe-Main, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware Drawing. Application January 20, 1936,

Serial No. 59,996. In Germany January 25,

6 Claims.

The present invention relates to polymethinedyestuffs.

We have found that acid polymethine-dyestufis, which are distinguished by a very good fastness to light and by clear shades, may be obtained by condensing a sulfonic acid of a hydrogenated heterocyclic nitrogen compound, such as, for instance, a dihydro-alpha-phenylindole, with an indoline compound containing in alpha-position to the nitrogen a reactive methylene-group, one hydrogen atom of which is replaced by the aldehyde-group; or by sulfonating the basic dyestuffs which are obtainable by condensing the aldehydo-compound with a hydrogenated heterocyclic nitrogen compound, or by simultaneously condensing and sulfonating both components in sulfuric acid.

The dyestuifs thus obtainable are new; there are obtained, for instance, the dyestuffs of the wherein the benzene nucleus R may contain substituents or may be condensed with a further benzene nucleus to form a naphthalene nucleus, wherein R1 means the radical of a hydrogenated heterocyclic compound of the group consisting of dihydroindoles and tetrahydroquinolines bound by its nitrogen atom to the =CH-group of the above formula and X means that the compounds may contain further sulfonic acid groups, and wherein the free bond of the SOs-group is attached to an aromatic nucleus of the molecule; and the salts of these compounds.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

(1) 8.5 parts of 1.3.3-trimethylindoline-2- methylene-omega-aldehyde and 18.? parts of the sodium salt of dihydro-Z-phenylindole-disulfonic acid (obtainable by sulfonating dihydro-2- phenylindole in fuming sulfuric acid containing 20 per cent. of sulfuric anhydride) are dissolved in 216 parts of sulfuric acid of 22 per cent. strength, and the whole is stirred for 8 hours at room temperature. The dyestufi which has separated in a powdery form is isolated and transformed by means of sodium carbonate into its sodium salt. It dyes wool very clear yellow tints of a very good fastness to light.

The dyestuff probably corresponds to the following formula:

(2) 12 parts of 1.3.3-trimethylinodli-ne-2- methylene-omega-aldehyde and 12 parts of dihydro-2-phenylindole are introduced at room temperature into 100 parts of fuming sulfuric acid containing 20 per cent. of sulfuric anhydride, and the whole is stirred for about 10 hours. The mass is then poured on ice and the dyestufi, probably a trisulfonic acid is transformed in the usual manner into its sodium salt. It dyes wool yellow tints of the same clearness and properties of fastness as those of the dyestuff described in Example 1.

(3) 10 parts of the basic dyestuff, which is obtainable by condensing 1.3.3-trimethyl-5- methoxyindoline 2 methylene omega aldehyde with tetrahydroquinoline (cf., for instance, the process described in U. S. specification Serial No. 756,893, filed December 10, 1934, in the name of Paul Wolif) are sulfonated in parts of sulfuric acid monohydrate for about 1 hour at 65 C. The mass is poured on ice and the dyestuif, probably a disulfonic acid, is then isolated in the form of its sodium salt. It dyes Wool vivid yellow tints of very good fastness to light.

(4) 10 parts of the basic dyestuff, which is obtainable by condensing 1.3.3-trimethy1-5-phenylindoline-Z-methylene-omega-aldehyde with dihydro-2-phenylindole (cf., for instance, the process described in the aforesaid U. S. specification), are sulfonated in 50 parts of sulfuric acid monohydrate in the course of 4 hours at 75 C. A dyestuff, probably a trisulfonic acid, is thus ob- 5 tained which, in the form of its sodium salt, dyes wool clear yellow tintsof very '-g oo;d-;fastness to light. i v

(5) parts of the basic dyestufi, which is obtainable by condensing 1.3.3-trimethyl-4.5-benZo- L 10 indo1ine-2-methylene-omega-a1dehyde with.dihy

dro-2-methylindole, are sulfonated atroorn t'emperature in fuming sulfuric acid-,cuntaining-ZO per cent. of sulfuric anhydride; the acid dyestufi lated in the usual manner.

(6) 10 parts of the basic dyestuff which is obtainable by condensing 1.3l3-trimethylindoline 2-methylene-omega-aldehyde with dihydro-2.5- dimethylindole, are sulfonated at 70 C; in ;$l furic acid monohydrate. The dyestuff formed, probably a disulfomcjacid. dyes wool brilliant greenish-yellow tints.-

' (7)' 10 parts of the"basic-;dyestuff, which is obtainable by condensing 5 1.3.13-trimeth5 'lindoline- 2-methylene-omega-aldehyde with dihydro-2- methyl-5-methoxyindole; are sulfonated with-sul furic acid monohydrate. The dyestufi formed has properties similar. to 'those of the dyestuif (8) 10 parts of the basic dyes'tuff which is obtainable by condensing 1.3.3-trim'ethyl '5-methoxyindoline-Z-methylene-omega-aldehyde with dihydro-Z.4.6-trimethy1indole, are sulfonated in fuming sulfuric acid containing: 10 per cent. of sulfuric anhydride. The acid dyestuff is isolated. It dyes wool tints somewhat more reddish than those of the dyestuff described in Example 6.

(9) 10 parts of 1.3.3-trimethylindoline-2-methylene-omega-aldehydeare condensed with 10.6 40 parts of dihydrO-Z-methylindosulfonic,acid in the presence of an acid condensing agent. The dyestuff obtainedgwhic'h probably has the following constitution: 3

thus formed, probably a trisulfonic acid, is isoerties of fastness. It corresponds probably to the following formula:

I -We claim: 7 1. The compoundsof the general formula:

I CH3 wherein R1 means the radical of a hydrogenated heterocyclic compound of the group consisting of dihydroindoles and tetrahydroquinolines bound by its nitrogen atom to the =CH-group of the above formula and X means a member of the group consisting of hydrogen and sulf-onic acid group and wherein the free bond of'the SO2- group is attachedto an aromatic nucleus of the molecule.

2. The compounds of the general formula:

wherein Y means a member of the group consisting of methyl and phenyl and X means a member of the group consisting of hydrogen and sulfonicacid group and wherein the free bond of the SOz-group is attached to an aromatic nucleus of the molecule.

.4 3. The compound of the formula:

SO2ONa being a dyestuif with very good properties of fastness.

4. The compound of the formula:

dyeing wool very clear yellow tints of very good fastness to light.

5. The compound of the formula:

dyeing wool very clear greenish-yellow tints. 6. The compounds of the general formula:

CH; 0- so,

wherein R1 means the radical of a hydrogenated heterocyclic compound of the group consisting of dihydroindoles and tetrahydroquinolines bound by its nitrogen atom to the =CH-group of the above formula, R2 means an aromatic radical of the group consisting of phenylene, methoxy-phenylene, phenyl-phenylene and naphthylene and X means a member of the group consisting of hydrogen and sulfonic acid group, and wherein the free bond of the SOz-group is attached to an aromatic nucleus of the molecule.

PAUL WOLFF. GUSTAV SCI-IAFER. 

